JP5143508B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition, a coating structure using the same, and a coating agent.

  Mesoporous metal oxide particles typified by mesoporous silica have a regular pore structure having a mesopore diameter of about 2 to 50 nm, and application studies using the pore structure are highly selective catalysts. It is widely promoted in the fields of control release technology, immobilization or stabilization of dyes and enzymes. There are also expectations for new functions by controlling the particle shape and size.

  On the other hand, the resin composition in which the silica compound is dispersed is not only from the viewpoint of the inexpensive, harmless (low toxicity) and versatility of the silica compound, but also high hardness, low refractive index, low dielectric constant, high transparency, etc. From the viewpoint of the above characteristics, it is widely used as a hard coat film, antireflection film, low dielectric constant material and the like. For example, it is known that a hard coat film of a resin composition in which colloidal silica is dispersed has higher strength than that of a resin alone.

  In Patent Document 1, mechanical strength, scratch resistance, and transparency are obtained by a coating material for forming a low refractive index film containing mesoporous silica particles having a porosity of 30 to 90% and an average primary particle diameter of 5 to 100 nm. It is described that a low refractive index film excellent in properties can be obtained.

In Patent Document 2, in a laminate obtained by laminating a base material, an intermediate layer, and a structure in this order, the intermediate layer contains mesoporous silica particles having an average primary particle diameter of 0.01 to 0.2 μm. In addition, it is described that the intermediate layer is excellent in adhesion and flexibility and has high durability.
JP 2004-83307 A JP 2005-119128 A

  An object of the present invention is to improve the hardness of a resin composition.

  The resin composition of the present invention contains a matrix resin and mesoporous metal oxide particles having a hollow structure dispersed in the matrix resin.

  In addition, the resin composition of the present invention is obtained by solidifying a matrix resin forming material in which mesoporous metal oxide particles having a hollow structure are dispersed.

The coating structure of the present invention is coated with a resin film,
The resin film is formed of a resin composition containing a matrix resin and mesoporous metal oxide particles having a hollow structure dispersed in the matrix resin.

  The coating agent of the present invention contains a matrix resin forming material and mesoporous metal oxide particles having a hollow structure dispersed in the matrix resin forming material.

  According to the present invention, the mesoporous metal oxide particles having a hollow structure are dispersed and contained, whereby the hardness can be improved.

  Hereinafter, embodiments will be described in detail.

(Resin composition)
The resin composition according to this embodiment contains a matrix resin and mesoporous metal oxide particles having a hollow structure dispersed therein.

  In this resin composition, by containing mesoporous metal oxide particles having a hollow structure dispersed therein, the hardness can be improved, and excellent transparency can be obtained. In particular, from the viewpoint of increasing the hardness, it is preferable that the matrix resin is also present in the mesopores of the mesoporous metal oxide particles and further in the hollow portion. This is because the bonding and interaction between the mesoporous metal oxide particles and the matrix resin is strengthened by the presence of the matrix resin in the mesopores and in the hollow portion of the mesoporous metal oxide particles, so that the hardness of the resin composition Is estimated to improve. Such a structure can be directly observed with a transmission electron microscope (TEM).

  The matrix resin is not particularly limited, and examples thereof include a thermosetting resin that is cured by heating, a photocurable resin that is cured by irradiation with light such as ultraviolet rays, and a thermoplastic resin. A curable resin is preferred. The matrix resin may be composed of a single type of resin, or may be composed of a mixture of a plurality of resins.

  Examples of the thermosetting resin and the photocurable resin include an epoxy resin, an unsaturated polyester resin, a phenol resin, a urea / melamine resin, a polyurethane resin, a silicone resin, and a diallyl phthalate resin.

  Examples of the epoxy resin include glycidyl ether type epoxy resins such as bisphenol A type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, cyclic aliphatic type epoxy resins, novolak type epoxy resins, naphthalene type epoxy resins, And cyclopentadiene type epoxy resin.

  Examples of the unsaturated polyester resin include orthophthalic acid unsaturated polyester resin, isophthalic acid unsaturated polyester resin, terephthalic acid unsaturated polyester resin, alicyclic unsaturated acid unsaturated polyester resin, and fatty saturated acid resin. Examples include unsaturated polyester resins, bisphenol-based unsaturated polyester resins, halogen-containing unsaturated polyester resins, and halogen-containing bisphenol-based unsaturated polyester resins.

  Examples of the phenol resin include a resol type phenol resin and a novolac type phenol resin.

  Examples of the thermoplastic resin include polyolefin resin, polyvinyl chloride (PVC) resin, vinylidene chloride resin, acrylonitrile / butadiene / styrene copolymer (ABS) resin, acrylonitrile / styrene copolymer (AS) resin, polystyrene ( PS) resin, methacrylic resin, polyvinyl alcohol (PVA) resin, styrenic block copolymer resin, polyamide (PA) resin, polyacetal (POM) resin, polycarbonate (PC) resin, modified polyphenylene ether (PEE) resin, thermoplastic polyester resin , Fluorine resin, polyphenylene sulfide (PPS) resin, polysulfone resin, amorphous arylate resin, polyetherimide (PEI) resin, polyethersulfone (PES) resin, polyetherketone (PEEK) Fat, liquid crystal polymer resin, polyamideimide resin, thermoplastic polyimide resin, and syndiotactic-based polystyrene resin.

  Examples of the polyolefin resin include polyethylene (PE) resin, polypropylene (PP) resin, α-olefin copolymer resin, polybutene-1 resin, polymethylpentene (PMP) resin, cyclic olefin polymer resin, and ethylene / vinyl acetate. Polymer (EVA) resin, EMAA resin, ionomer, etc. are mentioned.

  Examples of the polyamide resin include nylon 6, nylon 6,6, nylon 11, nylon 12, and the like.

  Examples of the thermoplastic polyester resin include polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polybutylene succinate (PBS) resin, and polylactic acid (PLA) resin.

  Fluororesin includes polytetrafluoroethylene (PTFE) resin, perfluoroalkoxyalkane (PFE) resin, perfluoroethylene propene copolymer (PFA) resin, ethylene-tetrafluoroethylene copolymer (ETFE) resin, polyvinylidene fluoride (PVdF) Resin, polychlorotrifluoroethylene (PCTFE) resin, ethylene-chlorotrifluoroethylene copolymer (ECTFE) resin, tetrafluoroethylene-perfluorodioxole copolymer (TFE / PDD) resin, polyvinyl fluoride (PVF) resin, etc. Can be mentioned.

  The weight average molecular weight of the matrix resin is preferably 200 to 100,000, and more preferably 500 to 10,000.

  The content of the matrix resin is preferably 30 to 95% by mass, and more preferably 50 to 85% by mass.

  The mesoporous metal oxide particles have an outer shell part mainly composed of a metal oxide, the inside of the particle is configured in a hollow structure, and a large number of pores communicating with the inner and outer sides are radially formed in the outer shell part. Has a structure. The outer shell of the mesoporous metal oxide particles and the hollow structure inside the particles can be confirmed by a transmission electron microscope (TEM). Further, the metal oxide constituting the outer shell part may have an organic group such as a hydrocarbon group having 1 to 22 carbon atoms or a phenylene group in which a part of hydrogen atoms may be substituted with fluorine atoms. Good.

  Examples of the mesoporous metal oxide particles having such a hollow structure include mesoporous silica particles, mesoporous titanium oxide particles, and mesoporous niobium oxide particles. The mesoporous metal oxide particles may be composed of a mixture of two or more metal oxides. Among these, mesoporous silica particles are preferable, but other metal elements such as Al, Ti, Nb, P, V, Fe, Co, Mo, Ni, Cu, Zn, and Ga are contained in the silica skeleton depending on applications. It may be.

  The average pore diameter of the mesoporous metal oxide particles is preferably 1 to 10 nm, more preferably 1.3 to 5.0 nm, and further preferably 1.5 to 2.5 nm. The mesoporous metal oxide particles having a particle diameter within ± 30% of the average pore diameter in the whole is preferably 70% or more, more preferably 75% or more, and 80% or more. Is more preferable. The average pore diameter and its distribution can be determined by the BJH method from the nitrogen adsorption isotherm obtained by nitrogen adsorption measurement.

  The average primary particle diameter of the mesoporous metal oxide particles is preferably 20 to 2000 nm, more preferably 50 to 1000 nm, and still more preferably 300 to 800 nm. The mesoporous metal oxide particles having a particle diameter within ± 30% of the average primary particle diameter of the whole is preferably 80% or more, more preferably 85% or more, and 90% or more. More preferably, it is 95% or more. The average primary particle size and the distribution thereof can be obtained by measuring the particle size of all particles in 5 fields including 20 to 30 particles in an observation photograph using a transmission electron microscope (TEM). it can.

  The average hollow part diameter of the mesoporous metal oxide particles is preferably 10 to 1000 nm, more preferably 50 to 800 nm, and still more preferably 200 to 500 nm. This average hollow part diameter can be calculated | required by measuring the hollow part diameter of all the particles in five visual fields in which 20-30 particles are contained in the observation photograph using a transmission electron microscope (TEM).

  The average outer shell thickness of the mesoporous metal oxide particles is preferably 30 to 700 nm, more preferably 50 to 500 nm, and even more preferably 70 to 400 nm. This average outer shell thickness can be obtained by measuring the outer shell thickness of all particles in five fields of view containing 20 to 30 particles in an observation photograph using a transmission electron microscope (TEM). it can.

  The ratio of the average outer shell thickness to the average primary particle diameter (average outer shell thickness / average primary particle diameter) is preferably 0.01 to 0.6, and preferably 0.05 to 0.5. More preferred is 0.1 to 0.4.

  The average aggregate particle diameter of the mesoporous metal oxide particles is preferably 0.1 to 10 μm, and more preferably 0.2 to 1.0 μm. This average agglomerated particle diameter is a median diameter in terms of volume measured using a laser scattering particle size distribution meter.

BET specific surface area of the mesoporous metal oxide particles is preferably 900~1500m ² / g, more preferably 1000~1300m ² / g. The BET specific surface area can be determined by measuring the BET specific surface area by a multipoint method using a specific surface area / pore distribution measuring apparatus.
The content of the mesoporous metal oxide particles is preferably 10 to 50% by mass, and more preferably 15 to 40% by mass.

  The mesoporous metal oxide particles include a hydrocarbon compound, an ester compound, a fatty acid having 6 to 22 carbon atoms, an alcohol having 6 to 22 carbon atoms, an oil agent such as silicone oil, a fragrance component, and an agrochemical group in a hollow portion inside the particle. Functional materials such as materials and pharmaceutical substrates, and polymers such as cationic polymers, nonionic polymers, and amphoteric polymers may be included.

  In addition to this, the resin composition according to this embodiment includes an antioxidant, a light stabilizer, an antistatic agent, a nucleating agent, a flame retardant, a plasticizer, a stabilizer, a colorant (pigment, dye), an antibacterial agent, and a surface activity. An agent, a high refractive index compound, a coupling agent, a release agent and the like may be contained. In addition, the resin composition according to the present embodiment may contain mesoporous metal oxide particles having no hollow structure together with mesoporous metal oxide particles having a hollow structure. It is preferable not to include mesoporous metal oxide particles that do not have.

  As a manufacturing method of the above mesoporous metal oxide particle, the following 1st and 2nd methods are mentioned, for example.

In the first method, (a) one or more selected from quaternary ammonium salts represented by the following general formulas (1) and (2) can be hydrolyzed, for example, at 0.1 to 100 mmol / L. An aqueous solution containing two or more metal oxide sources having different hydrolysis rates, for example, 0.1 to 100 mmol / L is prepared.
[R ¹ (CH ₃ ) ₃ N] ⁺ X ⁻ (1)
[R ¹ R ² (CH ₃ ) ₂ N] ⁺ X ⁻ (2)
(In the formula, each of R ¹ and R ² represents a linear or branched alkyl group having 4 to 22 carbon atoms, and X represents a monovalent anion.)
Examples of the alkyltrimethylammonium salt represented by the general formula (1) include butyltrimethylammonium chloride, hexyltrimethylammonium chloride, octyltrimethylammonium chloride, and the like, and also represented by the general formula (2). Examples of the dialkyldimethylammonium salt include dibutyldimethylammonium chloride, dihexyldimethylammonium chloride, dioctyldimethylammonium chloride, and the like.

  Next, the temperature of the aqueous solution is adjusted to, for example, 10 to 100 ° C. and stirred. Thereby, mesoporous metal oxide particles are precipitated, and a dispersion liquid in which mesoporous metal oxide particles are dispersed is obtained. In such mesoporous metal oxide particles, the metal oxide source having a low hydrolysis rate becomes oil droplets, and water does not enter the inside, preventing the hydrolysis reaction. The polymerization reaction proceeds with the component (a) incorporated on the surface of the oil droplets, and then the slowly hydrolyzed metal oxide source is gradually hydrolyzed and the dehydration condensation reaction proceeds. It is considered that alcohol formed by hydrolysis and water discharged from the dehydration condensation reaction are filled and deposited inside the particles.

  Then, the mesoporous metal oxide particles separated from the dispersion medium from the dispersion liquid are fired in an electric furnace or the like at, for example, 350 to 800 ° C. for about 1 to 10 hours. As a result, mesoporous metal oxide particles having a hollow structure are obtained because alcohol and water filled in the particles are volatilized.

  In order to prepare hollow mesoporous silica particles, when an alkoxysilane compound is used as two or more kinds of metal oxide sources that can be hydrolyzed and have different hydrolysis rates, the hydrolysis rate depends on the number of carbon atoms of the alkoxy group and silicon. It can be varied depending on the difference in the number of carbon atoms of the alkyl group bonded to the atom or the degree of bonding of a multimer in which a plurality of silicon atoms are bonded to each other by an organic bond such as alkylene. For example, the following compounds can be mentioned.

  Examples of the silica source having a high hydrolysis rate include one or more selected from tetraalkoxysilanes (tetramethoxysilane, tetraethoxysilane, etc.) having 1 to 3 carbon atoms in the alkoxy group.

  The silica source having a slow hydrolysis rate is selected from, for example, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, bistriethoxysilylmethane, bistriethoxysilylethane, and the like. 1 type or more is mentioned.

  In the second method, the component (a) in the first method is, for example, 0.1 to 100 mmol / L, and (b) the hydrolyzable metal oxide source is, for example, 0.1 to 100 mmol / L. (C) An aqueous solution containing, for example, 0.1 to 100 mmol / L of a hydrophobic organic compound or 0.01 to 10% by mass of a polymer is prepared.

  Next, the temperature of the aqueous solution is adjusted to, for example, 10 to 100 ° C. and stirred. Thereby, mesoporous metal oxide particles are precipitated, and a dispersion liquid in which mesoporous metal oxide particles are dispersed is obtained. Thus, the mesoporous metal oxide particles are precipitated because the hydrophobic organic compound or polymer becomes oil droplets, and the polymerization reaction proceeds in a state where the metal oxide source incorporates the component (a) on the surface of the oil droplets, This is considered to form an outer shell.

  Then, the mesoporous metal oxide particles are separated from the dispersion by a separation method such as a filtration method or a centrifugal separation method, washed with water or the like, and dried. Thereby, mesoporous metal oxide particles containing a hydrophobic organic compound or polymer in the hollow portion inside the particles can be obtained.

  In addition, if the mesoporous metal oxide particles separated from the dispersion medium from the dispersion liquid are baked, for example, at 350 to 800 ° C. for about 1 to 10 hours using an electric furnace or the like, the hydrophobic organic compound or polymer inside the particles is volatilized. By doing so, mesoporous metal oxide particles having a hollow structure can be obtained.

The hydrophobic organic compound of the second method means a compound that has low solubility in water and forms a phase separation with water. Preferably, the compound is dispersible in the presence of a quaternary ammonium salt described later. Examples of such a hydrophobic organic compound include compounds having a LogP _OW of 1 or more, preferably 2 to 25. Here, LogP is a 1-octanol / water partition coefficient of a chemical substance, and refers to a value obtained by calculation by the log K _OW method. Specifically, the chemical structure of a compound is decomposed into its constituents, and the hydrophobic fragment constants of each fragment are integrated (Meylan, WM and PH Howard. 1995. Atom / fragment contribution method for a reference octanol -water partition coefficients. See J. Pharm. Sci. 84: 83-92). Such hydrophobic organic compounds include, for example, hydrocarbon compounds, ester compounds, oils such as fatty acids having 6 to 22 carbon atoms, alcohols having 6 to 22 carbon atoms and silicone oils, perfume ingredients, base materials for agricultural chemicals, and pharmaceuticals. A functional material such as a base material can be given.

  Moreover, as a polymer, it is 1 or more types of polymers chosen from a cationic polymer, a nonionic polymer, and an amphoteric polymer, The polymer particle formed by emulsion-polymerizing an ethylenically unsaturated monomer is preferable. A substantially water-insoluble polymer is used.

  When preparing hollow mesoporous silica as metal oxide particles by the second method, it is easy to make a silane compound as a silica source that is a metal oxide source in production. 4 tetraalkoxysilanes can be used.

  Next, the manufacturing method of the resin composition which concerns on this embodiment is demonstrated.

  In the resin composition according to this embodiment, when the matrix resin is a thermosetting resin or a photocurable resin, a liquid resin material before curing is used as a matrix resin forming material, and mesoporous metal oxide particles having a hollow structure are used as the matrix resin. An example is a method in which after the dispersion, the matrix resin forming material is cured and solidified.

  When the matrix resin is a thermoplastic resin, (1) a mesoporous metal oxide particle having a hollow structure on a matrix resin forming material obtained by heating the matrix resin material to a fluid state (sometimes referred to as liquid) (2) The matrix resin material dissolved in a volatile solvent is used as a matrix resin forming material, and the mesoporous metal oxide particles having a hollow structure are dispersed in the solvent. (3) A method in which a monomer or intermediate polymer having fluidity is used as a matrix resin forming material, and mesoporous metal oxide particles having a hollow structure are dispersed therein and then polymerization is started and solidified. (4) A matrix resin-forming material is used which is fluidized before polymerization and is still solidified, and has a hollow structure. One mesoporous metal oxide particles are dispersed, a method of solidifying the like to complete the polymerization.

  In the present application, the “matrix resin forming material” means a fluid material that solidifies under a certain condition to form a matrix resin, for example, curing of a thermosetting resin or a photocurable resin. The previous liquid resin material, the thermoplastic resin material that has been made fluid by heating, the thermoplastic resin material dissolved in a volatile solvent, the thermoplastic resin pre-polymerization substance or the polymerization intermediate substance, etc. included.

  According to the above method for producing a resin composition, it is presumed that the matrix resin enters a hollow portion of at least a part of the hollow mesoporous metal oxide particles to increase the hardness. From the viewpoint of facilitating the entry of the matrix resin into the hollow part of the hollow mesoporous metal oxide particles, it is preferable that the matrix resin forming material solidifies with a reaction. Therefore, as a method for producing a resin composition, A method of forming a matrix resin forming material with a liquid resin material before curing of a thermosetting resin or a photocurable resin, and a method of forming a matrix resin forming material with a pre-polymerization material or a polymerization intermediate material of a thermoplastic resin. preferable.

  In addition, in the second method for preparing the hollow mesoporous metal oxide particles, the matrix resin-forming material is used as oil droplets, and the metal oxide source is taken in a state in which the quaternary ammonium salt is incorporated on the surface of the oil droplets. Polymerization is performed to obtain mesoporous metal oxide particles containing the matrix resin forming material in the hollow portion, and the metal oxide particles already containing the matrix resin forming material and the matrix resin forming material are mixed and solidified without firing. You may manufacture a resin composition by making it.

  When the resin composition is formed into a specific form or when the resin composition is used for coating, it is preferable to perform molding or the like in a state having fluidity or flexibility.

  If this resin composition is used, the coating structure coat | covered with the resin film formed with the said resin composition can be comprised. Depending on the application, the coating structure may be a single layer or a multilayer structure, and may be a self-supporting film without a substrate. However, from the viewpoint of the structural stability of the coating structure, a coating structure having a substrate is preferable. The form of the substrate also depends on the application and may be any form such as a substrate, a base film, particles, and fibers, but from the viewpoint of versatility, the substrate and the base film are preferable. Further, the material of the base material depends on its use and may be any material such as glass, alumina, metal, graphite, and resin, but glass, metal, and resin are preferable from the viewpoint of versatility.

  The coating structure coated with such a resin film is preferably transparent from the viewpoint of versatility. For example, the haze value obtained by the method described in the examples is preferably 30% or less, more preferably 20% or less, and more preferably 10%. % Or less is more preferable. Further, although depending on the type, material and application of the substrate, the coating structure coated with such a resin film preferably has a high hardness. For example, the pencil hardness obtained by the method described in the examples is 4H. The above is preferable, and 6H or more is more preferable.

  The coating structure coated with such a resin film can be applied to applications where high hardness is required for the resin film. In addition, for example, when the mesoporous metal oxide is mesoporous silica, it can be applied to applications that require a low refractive index, a low dielectric constant, and a low thermal expansion coefficient. Specifically, as a coating structure coated with such a resin film, for example, a structure in which a coating film on a surface to be coated is configured with this resin film, a hard coat film or an antireflection film on a lens surface is configured with this resin film. Examples include a structure, an interlayer insulating film of an electronic component material, and a structure in which a sealing material is formed of this resin film.

  In order to form the coating structure as described above, a coating agent containing a liquid matrix resin forming material and mesoporous metal oxide particles having a hollow structure dispersed therein may be used. Specifically, the coating agent may be applied to the coated surface, dried or heated, and irradiated with light. The coating agent can be applied according to a conventional method such as a spin coating method, a dip coating method, a bar coating method, a spray method, or a gravure coating method. Moreover, although the temperature of drying thru | or heating is dependent also on a composition of a coating structure, a material, and a use, from a viewpoint of productivity and ease of production, room temperature-300 degreeC is preferable, 50 degreeC-200 degreeC is more preferable, 70 degreeC More preferably, -130 ° C.

  The concentration of the mesoporous metal oxide having a hollow structure contained in the coating agent is preferably 0.1 to 50% by mass, and 0.5 to 40% by mass from the viewpoint of easy coating and performance of the obtained coating structure. More preferably, 0.7-30 mass% is still more preferable. In addition, the coating agent may contain a solvent (dispersion medium), and an alcohol solvent is preferable although it depends on the type of resin.

  In order to produce the coating agent, the liquid matrix resin forming material and the mesoporous metal oxide particles having a hollow structure may be mixed uniformly according to a conventional method such as magnetic stirring, blade stirring, or homomixer. From the viewpoint of expressing the performance of the resulting resin composition, it is preferable to allow the matrix resin-forming material to penetrate into the mesopores and hollow portions of the mesoporous metal oxide. Therefore, the mixing time is preferably 0.5 hours or more, and 1 hour. The above is more preferable. Further, penetration of the matrix resin forming material into the mesopores and hollow portions of the mesoporous metal oxide may be promoted by deaeration treatment or the like.

  Other coating agents include antioxidants, light stabilizers, antistatic agents, nucleating agents, flame retardants, plasticizers, stabilizers, colorants (pigments, dyes), antibacterial agents, surfactants, and high refractive index. You may contain a compound, a coupling agent, a mold release agent, etc.

(Methods such as various measurements)
Various measurement methods and the like in this example are as follows.

<Measurement of powder X-ray diffraction (XRD) pattern>
Using a powder X-ray diffractometer (trade name: RINT2500VPC manufactured by Rigaku Corporation), X-ray source: Cu-kα, tube voltage: 40 mA, tube current: 40 kV, sampling width: 0.02 °, divergence slit: 1 / Powder X-ray diffraction measurement was performed under the conditions of 2 °, divergent slit length: 1.2 mm, scattering slit: 1/2 °, and light receiving slit: 0.15 mm. A continuous scanning method with a scanning range of diffraction angle (2θ) of 1 to 20 ° and a scanning speed of 4.0 ° / min was employed. The measurement was performed by packing the pulverized sample in an aluminum plate.

<Measurement of average primary particle diameter, average hollow part diameter, and average outer shell part thickness>
Using a transmission electron microscope (TEM) (trade name: JEM-2100, manufactured by JEOL Ltd.), particles were observed at an acceleration voltage of 160 kV. The diameter, hollow diameter, and outer shell thickness of all particles in five fields of view containing 20-30 particles were measured on a photograph, and the average primary particle diameter, average hollow diameter, and average outer shell thickness were measured. Asked. In addition, observation was performed using what removed the excess thing by the blow from the sample adhering to Cu mesh (200-A mesh by Oken Corporation) with a carbon support film for high resolution.

<Observation of particle shape>
The particle shape was observed using an electrolytic emission type high resolution scanning electron microscope (trade name: FE-SEM S-4000, manufactured by Hitachi, Ltd.).

<Measurement of BET specific surface area and average pore diameter>
Using a specific surface area / pore distribution measuring device (trade name: ASAP2020 manufactured by Shimadzu Corporation), the BET specific surface area was measured by a multipoint method using liquid nitrogen, and a value was derived within a range where parameter C was positive. The BJH method was adopted for deriving the BET specific surface area, and the peak top was defined as the average pore diameter. The sample was pretreated for 5 hours at a temperature of 250 ° C.

<Measurement of average agglomerated particle size>
Conditions using a laser scattering particle size distribution meter (trade name: LA-920, manufactured by Horiba, Ltd.), a relative refractive index of 1.06, an ultrasonic intensity of 7, an ultrasonic irradiation time of 1 minute, a circulation speed of 4, and a dispersion medium of ethanol. Measured at room temperature, and the median diameter in terms of volume was defined as the average aggregated particle diameter.

(Preparation of mesoporous silica)
<Hollow mesoporous silica>
In a 2 L-separafull flask, 600 parts of ion-exchanged water, 99.5 parts of methyl methacrylate, and 0.5 part of methacryloyloxyethyltrimethylammonium chloride were added, and the temperature was raised to an internal temperature of 70 ° C.

  Next, 0.5 part of 2,2′-azobis (2-amidinopropane) dihydrochloride (trade name: V-50 manufactured by Wako Pure Chemical Industries, Ltd.) as a water-soluble initiator was dissolved in 5 parts of ion-exchanged water. The solution was added and stirred with heating for 3 hours.

  Thereafter, the mixture is further cooled by heating and stirring at 75 ° C. for 3 hours, and then the aggregate is filtered through a 200 mesh filter (aperture approximately 75 μm) to obtain a suspension of cationic polymer particles (solid content (effective Min) content 14%, average primary particle size 270 nm).

  Then, 6000 g of water, 2000 g of methanol, 45 g of 1M sodium hydroxide aqueous solution, 35 g of dodecyltrimethylammonium bromide, and 33 g of the suspension of cationic polymer particles prepared above were stirred in a 10 L flask.

  Next, 34 g of tetramethoxysilane was slowly added to the aqueous solution, stirred for 5 hours, and then aged for 12 hours.

  Next, the obtained white precipitate was filtered through a membrane filter having a pore size of 0.2 μm, washed with 10 L of water, and dried at a temperature of 100 ° C. for 5 hours.

  Subsequently, the obtained dry powder was heated to 600 ° C. at a rate of 1 ° C./min with an air flow (3 L / min) using a baking furnace (trade name: Superburn, manufactured by Motoyama Co., Ltd.). The organic component was removed by baking for 2 hours under the temperature condition of ° C.

  Then, the obtained calcined powder was subjected to dry crushing (passing a screen having a pore diameter of 0.2 mm at 20000 rpm) using a rotor speed mill (trade name: pulverisettel4 manufactured by FRITSCH) to obtain a hollow mesoporous silica powder. .

  This hollow mesoporous silica powder is characterized by a very strong XRD peak at d = 3.0 nm, weak XRD peaks at d = 1.7 nm and d = 1.5 nm in the powder X-ray diffraction (XRD) pattern. It was found that the mesopores of the silica powder have a hexagonal arrangement.

  Moreover, it was found from SEM observation that the hollow mesoporous silica had a spherical particle shape.

  Further, from TEM observation, this hollow mesoporous silica has a hollow structure, an average primary particle diameter of 590 nm, an average hollow part diameter of 270 nm, an average outer shell part thickness of 160 nm, and a uniform outer shell part exhibiting a hexagonal arrangement. It has been found that mesopores are present, and the mesopores penetrate radially from the hollow portion to the outside of the particles.

The hollow mesoporous silica had a BET specific surface area of 1120 m ² / g, an average pore diameter of 1.5 nm, and an average aggregate particle diameter of 0.70 μm.

<Solid mesoporous silica>
A solid mesoporous silica powder having no hollow structure was produced in the same manner as in the above-described method for producing hollow mesoporous silica except that the cationic polymer particles were not added.

  This solid mesoporous silica powder is characterized by a very strong XRD peak at d = 3.0 nm, a weak XRD peak at d = 1.7 nm and d = 1.5 nm in the powder X-ray diffraction (XRD) pattern. It was found that the mesopores of real mesoporous silica powder have a hexagonal arrangement.

  Moreover, it was found from SEM observation that the particle shape of the solid mesoporous silica was spherical.

  Further, from TEM observation, this solid mesoporous silica has a solid structure without a hollow structure, an average primary particle diameter of 500 nm, uniform mesopores showing hexagonal arrangement, and its mesofine It was found that the holes penetrated radially from the particle center to the outside of the particle.

The solid mesoporous silica had a BET specific surface area of 1200 m ² / g, an average pore diameter of 1.5 nm, and an average aggregate particle diameter of 0.65 μm.

<Amorphous mesoporous silica>
386 g of water was placed in a 1 L Teflon container, 113 g of dodecyltrimethylammonium bromide and 5.8 g of sodium hydroxide were dissolved in the water, and then colloidal silica (trade name, manufactured by Nissan Chemical Co., Ltd.) was stirred into this solution at room temperature. : Snowtex 20) 153 g was added dropwise over 7 minutes.

  Subsequently, after further stirring for 3 hours under a temperature condition of 40 ° C., aging was performed for 44 hours under a temperature condition of 140 ° C. using an autoclave.

  Next, the obtained white precipitate was filtered with a filter paper (No. 2), washed with 5 L of water, and dried under a temperature condition of 100 ° C. for 7 hours.

  Subsequently, the obtained dry powder was heated to 600 ° C. at a rate of 5 ° C./min with an air flow (3 L / min) using a baking furnace (trade name: Superburn, manufactured by Motoyama Co., Ltd.). The organic component was removed by baking at a temperature condition of 6 ° C. for 6 hours.

  Then, the obtained fired powder was lightly crushed in a mortar to produce amorphous mesoporous silica.

  For this amorphous mesoporous silica powder, in the X-ray powder diffraction (XRD) pattern, this is due to the very strong XRD peak at d = 3.4 nm, the weak XRD peak at d = 2.0 nm and d = 1.7 nm. It was found that the mesopores of the regular mesoporous silica powder had a hexagonal arrangement.

  In addition, SEM observation revealed that the amorphous mesoporous silica was an aggregate of amorphous particles.

Further, this amorphous mesoporous silica had a BET specific surface area of 1100 m ² / g, an average pore diameter of 2.0 nm, and an average aggregated particle diameter of 56 μm.

(Adjustment of coating agent and formation of resin film)
<Example 1>
Under stirring at room temperature, 148 g of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed with 252 g of 3-glycidoxypropyltrimethoxysilane (manufactured by Toray Dow Corning) and 41 g of tetraethoxysilane (manufactured by Toray Dow Corning). Thereafter, 103 g of 0.01 mol / L hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 30 minutes, and the resulting mixture was further stirred for 24 hours at room temperature to effect acid hydrolysis of alkoxysilane.

  Next, 347 g of methanol (manufactured by Wako Pure Chemical Industries, Ltd.), 103 g of 2-ethoxyethanol (manufactured by Wako Pure Chemical Industries, Ltd.) and a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., trade name: Silwet L-7001) ) 0.44 g and 4.43 g of curing catalyst acetylacetone aluminum (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed, and further stirred at room temperature for 1 hour to prepare a liquid silane matrix resin forming material.

  On the other hand, ultrasonic dispersion was applied for 10 minutes to obtain a methanol dispersion in which 0.5 g of the hollow mesoporous silica was dispersed in 9.5 g of methanol.

  Under stirring at room temperature, 0.20 g of this methanol dispersion was added to 1.06 g of the silane matrix resin forming material and stirred for 5 hours to prepare a silane coating agent containing hollow mesoporous silica.

  This silane-based coating agent was spin-coated (1000 rpm, 30 seconds) on an acrylic resin substrate (50 × 25 × 3 mm, manufactured by ASONE) using an ethanol-cleaned substrate, and then a temperature of 75 ° C. A silane resin film containing 30% by mass of hollow mesoporous silica was prepared by heating for 20 minutes under the conditions and further curing for 1 hour at a temperature of 110 ° C.

<Comparative Example 1>
A silane-based resin coating was prepared in the same manner as in Example 1 except that the solid mesoporous silica was used instead of the hollow mesoporous silica.

<Comparative example 2>
A silane-based resin coating was prepared in the same manner as in Example 1 except that the above amorphous mesoporous silica was used instead of the hollow mesoporous silica.

<Comparative Example 3>
A silane-based resin coating was prepared in the same manner as in Example 1 except that a commercially available colloidal silica (methanol silica sol manufactured by Nissan Chemical Industries, Ltd.) was used instead of the hollow mesoporous silica.

<Comparative example 4>
A silane-based resin coating was prepared in the same manner as in Example 1 except that no hollow mesoporous silica was added.

<Example 2>
10 g of 4-vinylcyclohexene dioxide (trade name: ERL4206, manufactured by Polyscience), 4.0 g of epoxy resin (trade name: DER736, manufactured by Polyscience), 26 g of nonenyl succinic anhydride (trade name: NSA, manufactured by Polyscience) To the mixed solution, 0.40 g of 2-dimethylaminoethanol (trade name: DMAE, manufactured by Polyscience) was added and stirred at room temperature for 5 minutes to prepare a liquid epoxy matrix resin forming material.

  An epoxy resin coating agent containing 20% by mass of hollow mesoporous silica was prepared by stirring 1.2 g of the epoxy matrix resin forming material and 0.30 g of the hollow mesoporous silica powder at room temperature for 1 hour.

  The epoxy resin coating agent containing the hollow mesoporous silica is spin-coated with a spin coater (manufactured by Able) on a glass slide (trade name: S1111, 76 × 52 × 1.3 mm, manufactured by Matsunami) washed with acetone. Then, the epoxy resin coating containing hollow mesoporous silica was prepared by heating and curing for 1 day at a temperature condition of 70 ° C. and further for 5 days at a temperature condition of 100 ° C.

<Comparative Example 5>
An epoxy resin coating was prepared in the same manner as in Example 2 except that the solid mesoporous silica was used instead of the hollow mesoporous silica.

<Comparative Example 6>
An epoxy resin coating was prepared in the same manner as in Example 2 except that the above amorphous mesoporous silica was used instead of the hollow mesoporous silica.

<Comparative Example 7>
An epoxy resin film was prepared in the same manner as in Example 2 except that a commercially available spherical silica powder (trade name: COSMO55, manufactured by Catalyst Kasei Co., Ltd.) was used instead of the hollow mesoporous silica.

<Comparative Example 8>
An epoxy resin film was prepared in the same manner as in Example 2 except that hollow mesoporous silica was not blended.

(Test evaluation method and results)
<Test method>
-Film formability-
About each of the said Examples 1 and 2 and Comparative Examples 1-8, the uniformity of the resin film was judged visually. And, in the appearance, the case of being uniform was marked with ◯, and the case of being non-uniform was marked with ×.

-Pencil hardness-
About each of the said Example 1 and 2 and Comparative Examples 1-8, according to JISK-5400, the highest pencil hardness when not scratching was investigated.

-Haze value-
About each of the said Example 1 and Comparative Examples 1-4, using the integrating sphere type | formula light transmittance measuring apparatus (Murakami Color Materials Laboratory make brand name: reflection transmission meter HR-100) prescribed | regulated to JIS-K7105. The haze value was measured.

<Test evaluation results>
The test evaluation results are shown in Table 1.

  According to Table 1, the resin films of Examples 1 and 2 containing hollow mesoporous silica, Comparative Examples 1 and 5 containing solid mesoporous silica, and Comparative Examples 3 and 7 containing silica sol have film-forming properties. On the other hand, it can be seen that the resin films of Comparative Examples 2 and 6 containing amorphous mesoporous silica and Comparative Examples 4 and 8 containing no silica have poor film formability.

  The resin film of Example 1 containing hollow mesoporous silica has a pencil hardness of 6H, while Comparative Examples 1 to 4 not containing hollow mesoporous silica have a pencil hardness of 5H, 4H, 4H, and 4H. . Moreover, the resin film of Example 2 containing hollow mesoporous silica has a pencil hardness of 4H, while Comparative Examples 5 to 8 not containing hollow mesoporous silica have a pencil hardness of 3H, 2H, 2H, and HB. It is. Therefore, it can be seen that the resin film of the example containing hollow mesoporous silica has higher hardness than the resin film of the comparative example not containing hollow mesoporous silica.

  The resin film of Example 1 containing hollow mesoporous silica and the resin films of Comparative Examples 1, 3, and 4 not containing hollow mesoporous silica had haze values of 5%, 4%, 3%, and 3%, While the transparency is excellent, the resin film of Comparative Example 2 has a haze value of 42%, indicating that the transparency is inferior.

  The present invention is useful for a resin composition, a coating structure using the same, and a coating agent.

Claims (12)

Epoxy resin, unsaturated polyester resin, phenol resin, urea melamine resin, polyurethane resin, diallyl phthalate resin, or silane resin thermosetting resin matrix resin, and average pore diameter with hollow structure dispersed in the matrix resin A mesoporous silica particle having a particle size of 1 to 10 nm, and a resin composition having a content of the mesoporous silica particle of 10 to 50% by mass ,
A resin composition in which the matrix resin is present in the hollow part of the mesoporous silica particles. The resin composition according to claim 1, wherein the mesoporous silica particles have an average primary particle diameter of 20 to 2000 nm. The resin composition according to claim 1 or 2, wherein the mesoporous silica particles have an average hollow part diameter of 10 to 1000 nm. The resin composition according to any one of claims 1 to 3, wherein the mesoporous silica particles have an average aggregate particle diameter of 0.1 to 10 µm. The mesoporous silica particles have a BET specific surface area of 900-1500 m. ² The resin composition according to any one of claims 1 to 4, which is / g. The resin composition according to any one of claims 1 to 5, wherein the mesoporous silica particles have an average outer shell thickness of 30 to 700 nm. Epoxy resin, unsaturated polyester resin, phenol resin, urea / melamine resin, polyurethane resin, diallyl phthalate resin, or silane-based thermosetting resin matrix resin forming material having an average pore diameter of 1 to 10 nm with a hollow structure mesoporous silica particles are dispersed Rutotomoni, obtained by solidifying what the matrix resin forming material in the hollow portion of the mesoporous silica particles are present the content of the mesoporous silica particles from 10 to 50 mass is % der Ru resin composition. The resin composition according to any one of claims 1 to 7, wherein the pores of the mesoporous silica particles have a hexagonal arrangement. A coating structure coated with a resin film formed of the resin composition according to claim 1. The coating structure according to claim 9, wherein the resin film has a pencil hardness measured based on JIS K5400 of 4H or more. The coating structure according to claim 9 or 10, wherein the resin film has a haze value of 30% or less measured based on JIS K7105. A coating agent used for forming a resin film having a coating structure according to any one of claims 9 to 11,
Epoxy resin, unsaturated polyester resin, phenol resin, urea / melamine resin, polyurethane resin, diallyl phthalate resin, or silane-based thermosetting resin matrix resin forming material having an average pore diameter of 1 to 10 nm with a hollow structure the mesoporous silica particles is, Rutotomoni dispersed so that the amount contained in the resin composition for forming the resin film after solidification is 10 to 50 mass%, the matrix resin forming material in the hollow portion of the mesoporous silica particles coating agent present.